Miscibility tests between sixty pairs of fluorous and organic solvents have been performed, and a number of biphasic systems based on hydrofluoroether solvents have been identified. Mutual solubilities of a series of fluorous and organic solvents have been measured to ascertain the compositions of the biphasic systems. A qualitative solvent tuning strategy based on solvent polarity and fluorophilicity/phobicity is introduced. Solvent tuning is then used to modulate the partition coefficients (P) of triarylphosphines with 0–3 fluorous tags. The results lay a foundation for future applications of these and related biphasic systems in catalysis and extraction.
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